Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F12/02—Monomers containing only one unsaturated aliphatic radical
  • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F17/00—Metallocenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

• the present invention relates to the preparation of alkylalumoxane-free catalyst compositions by abstraction of a leaving group from inert Group 4 metal compounds with a borane.
• the preceding formula I is referred to as the limiting, charge separated structure.
• the catalyst may not be fully charge separated. That is, the R group may retain a partial covalent bond to the metal atom, M.
• the catalysts may be alternately depicted as possessing the formula: L m MX n ⁇ R ⁇ BY 3 .
• the metal complex of formula I is useful for preparing vinyl aromatic monomers having a high degree of syndiotacticity as described in parent European Patent Application No. 92916748.4 (EP 0597961 A; WO 93/03067).
• substituted when used with reference to L or R means inert substituent groups, including such groups as aralkyl, alkaryl, haloalkyl, silylalkyl, haloalkyl, haloaryl, haloalkaryl, halosilyl, haloalkarylsilyl, and alkoxyalkyl.
• inert means noninterfering with the desired catalyst preparation or with the use of the resulting metal complex containing compound as a polymerization catalyst.
• compositions according to the present invention are those wherein m is 1, n is 2, and L is a cyclopentadienyl or substituted cyclopentadienyl group.
• cyclopentadienyl and substituted cyclopentadienyl groups for use according to the present invention are groups depicted by the formula: wherein: R' each occurrence is independently selected from hydrogen, halogen, R, NR 2 , PR 2 ; OR; SR or BR 2 , wherein R is as previously defined.
• R' is alkyl or haloalkyl of up to 6 carbons.
• Preferred delocalized ⁇ -bonding groups are cyclopentadiene and substituted cyclopentadiene, especially pentamethylcyclopentadiene.
• M is titanium
• X examples include R, halo, NR 2 , PR 2 , OR, SR, and BR 2 .
• X each occurrence is R, NR 2 or OR.
• Suitable metal derivative compounds include:
• Suitable borane compounds for use herein particularly include tris(fluoroaryl) and tris (trifluoromethyl substituted aryl) borane compounds, or other suitable inertly substituted borane compounds.
• Examples include tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, and tris(3,5-di(trifluoromethyl)phenyl)borane.
• perfluorinated compounds such as tris(pentafluorophenyl)borane.
• the catalyst is prepared by combining the metal compound, borane compound and AlR 3 in a suitable solvent at a temperature within the range from -100°C to 100°C, preferably 0 to 50°C.
• the presence of residual aluminum containing species in the catalyst system is not detrimental to catalyst performance.
• the catalyst system can also form in situ if the components thereof are added directly to the polymerization process and a suitable solvent or diluent, including condensed monomer, is used in said polymerization process. It is, however, preferred to form the catalyst in a separate step in a suitable solvent prior to adding the same to the polymerization step.
• the catalysts' components are generally sensitive to both moisture and oxygen and should be handled and transferred in an inert atmosphere such as nitrogen, argon or helium.
• the metal compound initially utilized may be a metal alkoxide or similar compound which by itself would not be suitable for use in combination with the borane.
• the improved catalyst of the present invention will, preferably, be prepared in a suitable solvent or diluent.
• Suitable solvents or diluents include any of the solvents known in the prior art including, but not necessarily limited to, straight and branched-chain hydrocarbons such as C 6-12 alkanes (hexane, heptane and octane); C 6-12 cyclic and alicyclic, aliphatic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, and methylcycloheptane; C 6-12 aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, xylene and decalin; and mixtures thereof.
• straight and branched-chain hydrocarbons such as C 6-12 alkanes (hexane, heptane and octane); C 6-12 cyclic and alicyclic, aliphatic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, and
• catalysts according to the present invention can be selected so as to produce polymer products that will be free of certain trace metals generally found in polymers produced with Ziegler-Natta type catalysts containing cocatalysts such as aluminum or magnesium based compounds.
• vinyl aromatic monomers can be polymerized in the presence of the catalyst as mentioned above.
• Suitable vinyl aromatic monomers which can be polymerized in the process of the present invention include those represented by the formula: wherein each R is independently hydrogen; an aliphatic, cycloaliphatic or aromatic hydrocarbon group having from 1 to 10, more suitably from 1 to 6, most suitably from 1 to 4, carbon atoms; or a halogen atom.
• Examples of such monomers include, styrene, chlorostyrene, n-butyl styrene, and p-vinyl toluene with styrene being especially suitable.
• Copolymers of styrene and the above vinyl aromatic monomers other than styrene can also be prepared.
• the polymerization may be conducted under slurry, bulk or suspension polymerization conditions or other suitable reaction conditions including solid, powdered reaction conditions.
• the polymerization can be conducted at temperatures of from 0°C to 160°C, preferably from 25°C to 100°C, more preferably from 30°C to 80°C, for a time sufficient to produce the desired polymer. Typical reaction times are from one minute to 100 hours, preferably from 1 to 10 hours. The optimum reaction time or reactor residence time will vary depending upon the temperature, solvent and other reaction conditions employed.
• the polymerization can be conducted at subatmospheric pressure as well as superatmospheric pressure, suitably at a pressure within the range of 1 to 500 psig (110 kPa-3.5 MPa). The use of ambient or low pressures, for example, 1-5 psig (110-135 kPa) is preferred in view of lower capital and equipment costs.
• the polymerization may be conducted in the presence of an inert diluent or solvent or in the absence thereof. In the latter event excess monomer serves as a diluent.
• suitable, nonreactive diluents or solvents include C 6-20 aliphatic, cycloaliphatic, aromatic and halogenated aliphatic or aromatic hydrocarbons, as well as mixtures thereof.
• Preferred nonreactive diluents comprise the C 6-10 alkanes, toluene and mixtures thereof.
• a particularly desirable diluent for the polymerization is iso-octane, iso-nonane or blends thereof such as Isopar-E®, available from Exxon Chemical Company. Suitable amounts of solvent are employed to provide a monomer concentration from 5 percent to 100 percent by weight.
• the molar ratio of the vinyl aromatic monomer to the catalyst may range from 100:1 to 1,000,000:1, preferably from 3,500:1 to 200,000:1.
• the catalyst may be used at a concentration with the range from 10 -7 to 10 -1 moles per liter of solvent.
• the monomers and solvents employed be of sufficiently high purity that catalyst deactivation does not occur.
• Any suitable technique for monomer purification such as devolatilization at reduced pressures, contacting with molecular sieves or high surface area alumina, and deaeration may be employed.
• a small amount of an aluminum trialkyl compound or similar scavenger may be added to the reaction mixture to protect the catalyst from deactivation by contaminants in the reaction mixture. Purification of the resulting polymer to remove entrained catalyst may also be desired by the practitioner.
• Purification of the resulting polymer prepared by the process of this invention is much easier than purification of polymer prepared by a conventional process since the process of this invention does not use polyalkylaluminoxane which is used in large quantities as cocatalyst in conventional processes.
• Entrained catalyst may generally be identified by residues of ash on pyrolysis of the polymer that are attributable to catalyst metal values.
• a suitable technique for removing such compounds is by solvent extraction, for example, extraction utilizing hot, high boiling chlorinated solvents, acids or bases, such as caustic, followed by filtration.
• solvent extraction for example, extraction utilizing hot, high boiling chlorinated solvents, acids or bases, such as caustic, followed by filtration.
• polymer purification is normally not necessary.
• a dry 2 ml volumetric flask was charged with 0.70 ml of a 0.0069M toluene solution of pentamethylcyclopentadienyltitanium tribenzyl under an argon atmosphere. Next, 97 ⁇ l of a 0.05M solution of tri(pentafluorophenyl) boron in toluene was added. Additional toluene was added to fill the flask.
• a dry 20 ml vial was charged with 10.0 ml (87.4 mmol) of purified styrene and 20 ⁇ l of a 1M solution of triisobutyl aluminum in toluene.
• the vial was capped with a TeflonTM coated septa and a metal crimp cap, and placed in a water bath at 70°C.
• 250 ⁇ l of the above catalyst composition was added, giving a total molar ratio of styrene:Ti:borane:triisobutyl aluminum of 145,000:1:1:33.
• the vial was removed from the water bath and the polymerization was stopped by the addition of 2ml of methanol.
• the off-white, insoluble product was washed with methanol and dried in-vacuo to obtain 5.2 gm of a resultant polymer.
• the polymer was insoluble in methylene chloride or other common solvents for atactic polystyrene, and had a melting point of 270.4°C (by DSC), consistent with polystyrene having a syndiotacticity of greater than 98 percent. Yield was 0.45 g, 5.0 percent.
• Molecular weight (Mw) determined by viscosity comparison of o-dichlorobenzene solutions of samples of known molecular weight was 221,000.
• Example 2 The reaction conditions of Example 2 were repeated excepting that the titanium compound used was pentamethylcyclopentadienyltrismethoxy titanium (4.8 ⁇ mol) and 26.5 ⁇ l of a 1M toluene solution of triisobutyl aluminum was added to the titanium compound before addition of the borane solution. The mixture of titanium compound, triisobutyl aluminum and tri(pentafluorophenyl)borane was allowed to interact while being stirred for 1.5 hours. The resulting catalyst solution was a medium brown color. The polymerization conditions of Example 1 were substantially repeated. The resulting polymer had a crystalline melting point of 270.2°C, consistent with a polymer having greater than 98 percent syndiotacticity. Yield was 11.5 percent. Mw as determined by viscosity comparison techniques was 814,000.
• Example 2 The reaction conditions of Example 2 were substantially repeated excepting that 48 ⁇ l of a 1M toluene solution of triisobutyl aluminum was added to the pentamethylcyclopentadienyltrismethoxy titanium compound before addition of the borane solution. In addition 1.25 ml of the 0.05M solution of tri(pentafluorophenyl) borane was used. The mixture of titanium compound, triisobutyl aluminum and tri(pentafluorophenyl)borane was allowed to interact while being stirred for 1.5 hours. The resulting catalyst solution was a medium brown color. The polymerization conditions of Example 2 were also repeated.
• the final molar ratio of styrene: Ti:borane:triisobutyl aluminum was 145,000:1:13:43.
• the resulting polymer had a crystalline melting point of 269.6°C, consistent with a polymer having greater than 98 percent syndiotacticity. Yield was 8.3 percent. Mw was 763,000.

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• Chemical Kinetics & Catalysis (AREA)
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• Polymers & Plastics (AREA)
• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Polymerization Catalysts (AREA)

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• 1991
  • 1991-08-05 US US07/740,529 patent/US5886117A/en not_active Expired - Fee Related
• 1992
  • 1992-07-10 DE DE69227787T patent/DE69227787T2/de not_active Expired - Fee Related
  • 1992-07-10 WO PCT/US1992/005823 patent/WO1993003067A1/en not_active Ceased
  • 1992-07-10 EP EP96111364A patent/EP0742226B1/de not_active Expired - Lifetime
  • 1992-07-10 EP EP92916748A patent/EP0597961A4/en not_active Withdrawn
  • 1992-07-10 CA CA002113177A patent/CA2113177A1/en not_active Abandoned
  • 1992-07-10 AT AT96111364T patent/ATE174031T1/de not_active IP Right Cessation

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